4-acyloxy-5-pyrazolones



United States Patent 6 Claims ABSTRACT OF THE DISCLOSURE4-acyloxy-5-pyrazolones are two-equivalent magenta dye-forming couplersused advantageously in color photography.

This is a divisional application of US. Patent application Ser. No.247,302, Couplers for Color Photography, filed Dec. 26, 1962, now US.Patent 3,311,476.

This invention relates to photography and particularly to compoundswhich form dyes upon coupling with oxidized color developing agent andto photographic elements containing these compounds.

The formation of colored photographic images by the coupling of oxidizedaromatic primary amino developing agents with color forming or couplingcompounds is well known. In these processes the subtractive process ofcolor formation is ordinarily used and the image dyes are intended to becyan, magenta and yellow, the colors that are complementary to theprimary colors. Usually phenol or naphthal couplers are used to form thecyan dye image, pyrazolone couplers are used to form the magenta dyeimage and couplers containing a methylene group having one or twocarbonyl groups attached to it are used to form the yellow dye image.

In these color developing processes the color forming coupler may beeither in the developer solution or incorporated in the light-sensitivephotographic emulsion layer so that during development it is availablein the emulsion layer to react with the color developing agent that isoxidized by silver image development. Ditfusable' type couplers are usedin color developer solutions. Fischer-type couplers and hydrophobiccouplers are incorporated in photographic emulsion layers. When the dyeimage formed is to be used in situ, couplers are selected which formnondilfusing dyes. The dye image used for image transfer processesshould be dilfusable but capable of being mordanted or fixed in thereceiving sheet. For this purpose a coupler is selected which willproduce this type of dye.

Conventional color-forming couplers are four-equivalent, that is, theyrequire the development of four molecules of exposed silver halide inorder to supply one molecule of oxidized color developing agent that isfree to couple and form one molecule of dye. Two-equivalent couplersrequire the development of only two molecules of exposed silver halideto bring about the formation of one molecule of dye. Two-equivalentcouplers are very desirable for color photography, since only one-halfthe usual amount of silver halide is needed and the lightsensitivecoatings can thus be made thinner. Certain of the availabletwo-equivalent couplers tend to produce more stain than is desired, andothers have not had the desired coupling reactivity, New classes oftwo-equivalent couplers are needed.

It is, therefore, an object of my invention to provide a new class ofcolorless two-equivalent cyan-forming and magenta-forming couplers whichhave a high degree of reactivity.

Another object of my invention is to provide valuable acyloxysubstituted two-equivalent couplers for forming cyan dye images andmagenta dye images that have good spectral absorption characteristics,and good stability to prolonged exposure to light, heat and highhumidity.

Another object is to provide acyloxy substituted twoequivalent couplerswhich have good coupling reactivity and which include the diifusibletype coupler, the Fischer type and the hydrophobic type couplers whichare readily incorporated in light-sensitive hydrophilic colloid-silverhalide emulsion layers in a wide range of coupler to solvent ratios.

Still another object is to provide photographic hydrophiliccolloid-silver halide emulsion layers containing my acyloxy substitutedtwo-equivalent couplers.

Still further objects will be apparent from the following specificationand claims.

These and other objects are accomplished by the use of my acyloxysubstituted two-equivalent couplers. My new class of couplers includethe magenta-forming couplers of formula:

I /N=C-R4 RL-N\ (J-CH II I 0 5 0:0 1,. and the cyan-forming couplers ofthe formulas: II (|)H wherein R represents a group selected from theclass consisting of an alkyl group having from 1 to 22 carbon atoms,e.g., methyl, 3-pentadecylphenoxymethyl, ethyl, phenylethyl, n-propyl,isopropyl, a-(2,4-di-tertamylphenoxy)propyl, a-sulfobutyl sec-butyl,tert-butyl, docosyl, chloromethyl, trifluoromethyl, 2-hydroxymethyl,flcarboxyethyl, 2 (2,4,6 trichlorophenyl)ethyl, 2-aminoethyl,a,a-dimethylbutyl, a-methoxy-a-methyloctyl, ocpropyl-a-octyldocosyl, a,x-dibutyldocosyl, a,a-di -decylundecyl, a,a-di-tert-butyldodecyl,a,a-di-sec-butylpentadecyl, etc., a terpenyl group, e.g.,7,7-dimethylnorbornyl, 2-alkyl-7,7-dimethylnorbornyl radicals in whichthe alkyl group has from 1 to 18 carbon atoms, such as methyl, butyl,octadecyl, etc., for example, 2-methyl-7,7-dimethylnorbornyl,2-octadecyl-7,7-dimethylnorbornyl, etc., a 2- aryl-7,7-dimethylnorbornylradical, such as 2-phenyl-7,7- dimethylnorbornyl,2-tolyl-7,7-dimethylnorbornyl, etc. an aryl group, e.g., phenyl,3-(2-carboxybenzamido)phenyl, 3-(B-sulfopropionamido)phenyl, a-naphthyl,S-naphthyl, 2,4,6-trichlorophenyl, 4-ethoxyphenyl, 4-bromophenyl, 4-fluorophenyl, 3- a- 2,4-di-tert-amylphenoxy) butyramido] phenyl,3-['y-(2,4-di-tert-amylphenoxy)butyramido1phenyl, etc., a heterocyclicradical, e.g., a benzofuranyl group,

3 4 a furanyl group, a thiazolyl group, a benzothiazolyl group, acyclopentene ring, a thiazole ring, an oxazole ring, an anaphthothiazolyl group, an oxazolyl group, a benzoxaimidazole ring, apyridine ring, a pyrrole ring, a tetrazolyl group, an imidazolyl group,a benzimidazolyl group, hydropyridine ring, etc. a quinolinyl group,etc.; R represents the hydrogen atom, My two-equivalent couplers arecharacterized by having a primary, secondary or tertiary alkyl grouphaving from an acyloxy group on the coupling position of the coupler 1to 22 carbon atoms, e.g., methyl, propyl, isopropyl, nwhich gives themgood coupling reactivity and other valubutyl, secondary butyl, tertiarybutyl, hexyl, dodecyl, doable properties. Some of my nondiffusablecouplers have cosyl, 2-chlorobutyl, 2-hydroxyethyl, 2-phenylethyl, 2-good coupling reactivity when incorporated in emulsion2-(2,4,6-trichlorophenyl)ethyl, 2-arninoethyl, etc., an aryl layers Withno high-boiling coupler solvents, while the group, e.g., phenyl,4-methylphenyl, 2,4,6-trichlorophenothers are dispersed to advantage inhigh-boiling solvent yl, 3,5 dibromophenyl, 4 trifluoromethylphenyl, 2trisolutions in a wide range of coupler to solvent ratios.

fluoromethylphenyl, 3-trifluoromethylphenyl, naphthyl, 2- The followingrepresentative magenta-forming and cychloronaphthyl, 3-ethylnaphthyl,etc. aheterocyclic group, an-forming couplers will illustrate but notlimit my ine.g., a benzofuranyl group, a furanyl group, a thiazolylvention.

group, a benzothiazolyl group, a naphthothiazolyl group, MAGENTADYEFORMING COUPLERS an oxazolyl group, a benzoxazolyl group, anaphthoxazolyl 1- 11 1-3-11 th 1-4-a to: -5-

'. 1 group, a pyrldyl group, a qumolmyl group, etc.; R repp eny 1 e y Cem mm one resents the hydrogen atom, a primary, secondary or (1) N:OCHtertiary alkyl group having from 1 to 22 carbon atoms Ca s-N as definedfor R an aryl group as defined for R 21 heterocyclic group as definedfor R attached directly to 1 the coupler molecule, an amino group, e.g.,amino, meth- 0 000cm ylamino, diethylamino, docosylamino, phenylamino,tolylamino 4 (3'sulfobenzamido)anflino 4 cyanophenyla'1-(2,4,(3'tricl1lo1'0phenyl)-3-(4-nitroanilino)-4-stearoyl0xymino,Z-trifiuorornethyl phenylarnino, benzothiazolamino, 25 -ny etc., acarbonamido group, e.g., an alkylcarbonamido (2) Cl group, such asethylcarbonamido, decylcarbonamido, NO2 phenylethylcarbonamido, etc., anarylcarbonamido group, G1- N such as phenylcarbonamido,2,4,6-trichlorophenylcarbonamido, 4-methylphenylcarbonamido,2-ethoxyphenylcar- G1 [5 6 H bonamido, 3-[u-(2,4-di tertamylphenoxy)acetamido] 1- (2,4,Gtrichlorophenyl) -3{3- a-(2,4-di-tert-amylphenoxy) acetamido]-benzamid0}-4-acetoxy-5-pymz0loucbenzamido, naphthylcarbonamido, etc., a heterocyclic car- C -F RM N C PER bonarnido group, such as thiazolylcarbonamido, benzothi-4-benz0yloxypl1en0l azolylcarbonamido, naphthothiazolylcarbonamido, oxa-4 zolylcarbonamido, benzoxazolylcarbonarnido, imidazolyl- 0Hcarbonamido, benzimidazolylcarbonamido, etc., a sulfonamido group, e.g.,an alkylsulfonamido group, such as butylsulfonamido, docosylsulfonamido,phenylethylsulfonamido, etc., an arylsulfonamido group, such asphenylsulfonamido, 2,4,6-trichlorophenylsulfonamido, Z-methoxyl 000 Hphenylsulfonamido, 3-carboxyphenylsulfonamido, naph- O 6 5thylsulfonarnido, etc., a heterocyclic-sulfonamido group, 4acOt0xyphen01 such as thiazolylsulfonamido, benzothiazolylsulfonamido,(5) OH imidazolylsulfonamido, benzimidazolylsulfonamido,pyridylsulfonamido, etc., an alkylsulfamyl group, e.g., propylsulfamyl,octasulfamyl, pentadecylsulfamyl, octadecylsulfamyl, etc., anarylsulfamyl, such as phenylsulfamyl, 2,4,6- trichlorophenylsulfamyl,2-methoxyphenylsulfamyl, naphthylsulfamyl, etc., a heterocyclic sulfamylgroup, such as a thiazolylsulfamyl, a benzothiazolylsulfamyl, anoXazolyl- L sulfamyl, a benzimidazolylsulfamyl, a pyridylsulfamyl fgroup, etc., an alkylcarbamyl, such as ethylcarbamyl, oc- CH3tylcarbamyl, pentadecylcarbamyl, octadecylcarbamyl, etc.,

an arylcarbamyl, such as phenylcarbamyl, 2,4,6-trichlorophenylcarbamyl,etc., a heterocyclic carbamyl group, such (6) O as a thiazolylcarbamyl,a benzothiazolylcarbamyl, an oxazolylcarbamyl, an imidazolylcarbamyl, abenzimidazolyl- K/ C0OH 1-hytlroxyAvacetoxy-2-naphthoic acid carbamylgroup, etc.; R R R R and R each represent any of the groups defined by Rand W represents the nonmetallic atoms necessary to form a fused 5- or6- membered ring, such as a benzene ring, a cyclohexene ring, 0 C 06-acetamido-2-ehloro-4- [a- 2,4tert-amylphenoxy) acetoxy] 3-methylpheuol(7) H 01 NH0 0 C H:

| OCOCHZO- -CnHi1-t hHu-t 1-hydroxyA-stearoyloxy-2-naphtlioic acid I 0CO C|7H35 1-l1ydroxy-4-acetoxy-N- [6- (2,4-di-tert-amylphen0xy) -butyl]2naphthamide 0 lNHCHzCHzCHzCHzOQ-Crlin(t) OCOCHs naphthanilide (10) (Hi0 0151131 (IJOOH u l Q oorr OCOCHs The diffusible couplers of myinvention, such as magenta-forming couplers Nos. 1 and 2 andcyan-forming couplers Nos. 4 and are used to advantage in colordeveloper solutions used to color develop light-sensitive elements usedfor color photography which do not contain the color-forming coupler.Any of the well known primary aromatic amino color-forming silver halidedeveloping agents such as the phenylenediamines, e.g.,diethyl-pphenylenediamine hydrochloride, monomethyl-p-phenylenediaminehydrochloride, dimethyl-p-phenylenediamine hydrochloride,2-amino-5-diethylaminotoluene hydrochloride, 2 amino 5 (Nethyl-N-lauryl) toluene, N-ethyl-B-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate,N-ethyl-fl-methanesulfonamidoethyl-4-aminoaniline 4-N-ethyl-N-fl-hydroxyethylarninoaniline, etc., the p-aminophenols and theirsubstitution products where the amino group is unsubstituted may be usedin the alkaline devel; oper solution with my couplers. Various othermaterials may be included in the developer solutions depending upon theparticular requirements, for example, an alkali metal sulfite,carbonate, bisulfite, bromide, iodide, etc., and the thickening agentsused in viscous developer compositions such as are described incopending Whitmore and Mader U.S. Ser. No. 222,105, filed Sept. 7, 1962.The following is a typical developer solution given to illustrate butnot limit the invention.

Water to 1000.0

The diifusible couplers of my invention are used to advantage inemulsion layers when incorporated by the methods described by Mannes etal. U.S. Patent 2,304,- 940, issued Dec. 15, 1940.

Cyan coupler No. 6 illustrates a type of coupler that is used toadvantage in color developer solutions (with image-forming couplers) ascompeting couplers, since the dyes formed are diifusible and are washedout of the emulsion layer during processing. Similarly, other couplersof my invention can be used as competing couplers providing asolubilizing group or groups are present on the R R R R R R or R groups.

The other coupler examples used to illustrate my invention arenondifiusing and are used to advantage in photographic emulsion layers.Cyan couplers No. 8 and No. 10 illustrate those that are incorporated asFischer type couplers. The other nondiffusing couplers are incorporatedin emulsion layers by methods such as are described by Mannes et al.U.S. Patent 2,304,939, issued Dec. 15, 1942, Jelley et al. U.S. Patent2,322,027, issued June 15 1943, etc., in which high-boiling organicsolvents are used to dissolve the coupler, and by methods described inVittum et al. U.S. Patent 2,801,170, and Fierke et .al. U.S. Patent2,801,171, both issued July 30, 1957, and Julian U.S. Patent 2,949,360,issued Aug. 16 1960 in which lowboiling or water-soluble organicsolvents are used with or in place of the high-boiling solvent. Not onlycan emulsion layers containing my couplers be made thinner because theyrequire only one-half the silver halide required by conventionalcouplers (i.e. four-equivalent couplers) but some of my couplers aresufliciently reactive that they do not require any high-boiling couplersolvent that is usually required by couplers. Thin image-forming layersare very desirable because they cause less light scattering and producesharper images.

My nondiffusing cyan coupler No. 8 forms diffusible dye images uponcolor development and is used to advantage either in image transferelements or in emulsion layers that contain my coupler as anonimage-forming competing coupler along with an image-forming coupler.

The other nondiflusing couplers used to illustrate my invention formnonditfusing dyes and are used to advantage in any photographic elementwhere incorporated image-forming couplers are desired.

My couplers are used in the color development of photographichydrophilic colloid-silver halide emulsion layers of the developing-outtype either in the color developer solution or in the emulsion layer.The emulsions may contain silver chloride, silver bromide, silveriodide, silver chlorobromide, silver bromoiodide, silverchlorobromoiodide, etc., as the light-sensitive material.

Hydrophilic colloids used to advantage include gelatin, colloidalalbumin, a cellulose derivative, or a synthetic resin, for instance, apoyvinyl compound. Some colloids which may be used are polyvinyl alcoholor a hydrolyzed polyvinyl acetate as described in U.S. Patent 2,286,215,of Lowe; a far hydrolyzed cellulose ester, such as cellulose acetatehydrolyzed to an acetyl content of 1926%, as described in U.S. Patent2,327,808 of Lowe and Clark, a water-soluble ethanolamine celluloseacetate as described in U.S. Patent 2,322,085 of Yutzy; a polyacrylamidehaving a combined acrylamide content of 3060% and a specific viscosityof 0.251.5 on an irnidized polyacrylamide of like acrylamide content andviscosity as described in U.S. Patent 2,541,474 of Lowe, Minsk andKenyon; zein as described in U.S. Patent 2,563,791 of Lowe; a vinyl.alcohol polymer containing urethane carboxylic acid groups of the typedescribed in U.S. Patent 2,768,154 of Unruh and Smith, or containingcyanoacetyl groups, such as vinyl alcohol-vinyl cyano-acetate copolymeras described in U.S. Patent 2,808,331 of Unruh, Smith and Priest; or apolymeric material which results from polymerizing a protein or .asaturated acylated protein with a monomer having a vinyl group asdescribed in U.S. Patent 2,852,382 of Illingsworth, Dann and Gates.

The emulsions used in the photographic element of my invention can bechemically sensitized by any of the accepted procedures. The emulsionscan be digested with naturally active gelatin, or sulfur compounds canbe added, such as those described in Sheppard U.S. Patent 1,574,944;Sheppard and Punnett U.S. Patent 1,623,499; and Sheppard and BrighamU.S. Patent 2,410,689.

The emulsions can also be treated with salts of the noble metals, suchas ruthenium, rhodium, palladium, iridium and platinum. Representativecompounds are ammonium chloropalladate, potassium chloroplatinate, andsodium chloropalladite, which are used for sensitizing in amounts belowthat which produces any substantial fog inhibition, as described inSmith and Trivelli U.S. Patent 2,448,060 and as antifoggants in higheramounts, as described in Trivelli and Smith U.S. Patents 2,566,245 and2,566,263.

The emulsions can also be chemically sensitized with gold salts asdescribed in Waller, Collins and Dodd U.S. Patent 2,399,083 orstabilized with gold salts as described in Damschroder U.S. Patent2,597,856 and Yutzy and Leermakers U.S. Patent 2,597,915. Suitablecompounds are potassium chloroaurite, potassium aurithiocyanate,potassium chloroaurate, auric trichloride and 2-aurosulfobenzothiazolemethochloride.

The emulsions can also be chemically sensitized with reducing agents,such as stannous salts (Carroll US. Patent 2,487,850), polyamines, suchas diethylene triamine (Lowe and Jones U.S. Patent 2,518,698),polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925), orbis(;8-aminoethy1) sulfide and its watersoluble salts (Lowe and JonesU.S. Patent 2,521,926).

The emulsion can also be chemically sensitized with cyanine andmerocyanine dyes, such as those described in Brooker U.S. Patents1,846,301, 1,846,302, and 1,942,854, White U.S. Patent 1,990,507;Brooker and White U.S. Patents 2,112,140, 2,165,338, 2,493,747, and2,739,964, Brooker and Keyes U.S. Patent 2,493,748; Sprague U.S. Patents2,503,776 and 2,519,001, Heseltine and Brooker U.S. Patent 2,666,761;Heseltine U.S. Patent 2,734,900; VanLare U.S. Patent 2,739,149, andKodak Limited British 450,958.

The emulsions may also contain speed-increasing compounds of thequaternary ammonium type of Carroll U.S. Patent 2,271,623, Carroll andAllen U.S. Patent 2,288,226, and Carroll and Spence U.S. Patent2,334,864, and the polyethylene glycol type of Carroll and Beach U.S.Patent 2,708,162.

The above-described emulsions can be coated on a wide variety ofphotographic emulsion supports. Typical supports include cellulosenitrate film, cellulose acetate film, polyvinyl acetal film, polystyrenefilm, polyethylene terephthalate film, polyethylene film, polypropylenefilm, and related films of resinous materials, as well as paper, glassand others.

Usually my emulsions are coated on photographic supports in the form ofmultilayer color photographic elements wherein at least threedifferently sensitized emulsion layers are coated over one another onthe support. Usually the support is coated in succession with aredsensitive layer, a green-sensitive layer and a blue-sensitive layereither with or without a Carey Lea filter layer between theblue-sensitive and green-sensitive layers. The three ditferently colorsensitized layers may be arranged in any other order over one anotherthat is desirable; however, the Carey Lea filter layer obviously wouldnot be put over the blue-sensitive layer. Preferably, theselight-sensitive layers .are arranged on the same side of the support.

Elements made for image transfer processing may use a separate receptionsheet which is contacted with the light-sensitive layer during itsdevelopment or the reception layer may be an integral part of thelight-sensitive element. Any of the support materials mentionedpreviously may be used for a separate reception sheet. The receptionlayer comprises a hydrophilic colloid layer containing a cationicmordant, e.g., the polymers of amino guanidine derivatives of vinylmethyl ketone such as described in Minsk U.S. Patent 2,882,156, grantedApr. 14, 1959. Other mordants include the 2-vinyl pyridine polymermetho-p-toluene sulfonate and similar compounds described in Sprague etal. U.S. Patent 2,484,430, granted Oct. 11, 1949, and cetyl trimethylammonium bromide, etc. Particularly effective mordanting compositionsare described in copending applications of Kneckel et al. U.S. Ser. No.211,095, filed July 19, 1962, and Bush U.S. Ser. No. 211,094, filed July19, 1962. Additional variations of the image transfer elements andprocesses in which couplers of my invention (such as 8) can be used toadvantage, are described in copending application of Whitmore and MaderU.S. Ser. No. 222,105, filed Sept. 7, 1962.

The following Examples 1 and 2 will serve to illustrate the use of mymagenta-forming couplers but it is understood that my invention is notto be limited thereby.

EXAMPLE 1 A magenta-forming developer solution having the formula:

Grams Sodium sulfite 2 2-amino-S-diethylaminotoluene HCl 2 Sodiumcarbonate 20 Potassium bromide 2 Magenta coupler No. 1 2

Water to 1 1. pH adjusted to 11.5 with NaOH.

was used to color develop a magenta image in a strip of light imageexposed silver halide emulsion. The silver in the strip was converted tosilver halide by treating it with a ferricyanide-bromide bleach and thenthe silver halide was removed by treating the strip with a hypo fix bathto leave a good magenta dye image.

EXAMPLE 2 Processing solution: Time in minutes Color developer 11.5 Acidstop bath 6.0 Formalin hardener 4.0 Water wash 4.0 Ferricyanide bleach6.5 Water wash 4.0 Hypo fix 4.5 Water wash 8.0

Color developer Benzyl alcohol ml 5.00 Sodium hexametaphosphate g 2.50Sodium sulfite g 1.85 Sodium bromide g 1.40 Potassium bromide mg 0.50Sodium hydroxide g 13.10 Borax 39.60

4-amino-N-ethyl-3-methyl-N-,8methylsulfonamidoethylaniline g 50.00

Water to make 1000.0 ml.

Acid stop bath Acetic acid (glacial) ml 8.6

Water to make 1000.0 m1.

Formaline hardener F-ormalin (37% by weight formaldehyde in Water tomake 1000.00 ml.

Examples 3, 4 and 5 will serve to illustrate the use of my cyan-formingcouplers, but are not to limit the invention.

EXAMPLE 3 A cyan-image-forming developer solution having the formula:

Grams Sodium sulfite 2 2-amino-5-diethylaminotoluene HCl 2 Sodiumcarbonate 20 Potassium bromide 2 Cyan coupler No. 4 2

Water to 1 1. pH adjusted to 11.5 with NaOH.

was used to develop a cyan image in a light image exposed silver halideemulsion layer. The developed layer was treated with a conventionalbleach and hypo fix to leave a good cyan dye image.

EXAMPLE 4 Cyan-forming coupler No. 7 dispersed in coupler solventunderwent a coupling reaction with oxidized color developing agent toform a nondiifusing cyan image dye.

EXAMPLE 5 A good cyan dye image is obtained by color developing a lightimage exposed gelatino-silver bromide emulsion containing mycyan-forming coupler No. 9 dissolved in tri-o-cresylphosphate. Thecoating contains 400 mg. gelatin/ft. 150 mg. Ag/ft. 60 mg. coupler/ft.and 30 mg. solvent/1L The process is described in Example 2.

Similarly, a good cyan dye image is produced by color developing a lightimage exposed emulsion containing my cyan-forming coupler No. 10. Thisis a Fischer-type coupler and does not require coupler solvent forincorporating it in the emulsion. The emulsion is like that describedpreviously in this example except that no coupler solvent is used.

A light-image exposed emulsion containing cyan-forming coupler No. 8instead of No. 10 produces a good ditfusible cyan dye image when it isprocessed by contacting it for 7 minutes at 80 F. with a mordantcontaining receiving sheet that is presoaked in the following developersolution.

Gnams Sodium carbonate monohydrate 22.000 Ascorbic acid 0.385 Potassiumbromide 0.825 Sodium sulfite 2.000 4-N-ethyl-N-fi-hydroxyethylaminoaniline 11.000 Water to 1100.000 ml. pH 11.0

The preparation of my magenta-forming couplers having Formula I isillustrated by the preparation of coupler 1 starting with thefour-equivalent parent pyr'azolone couplers as follows:

1-phenyl-3-methyl-4- (4-dimethylaminophenylimino S-pyrazolone To asolution of 261 g. of 1-phenyl-3-methy1-5-pyrazolone (US. Patent1,969,479) in 2 l. of ethyl alcohol was added 8 ml. of 5% sodiumcarbonate solution and a solu tion of 225 g. of 4-nitrosodimethylanilinein 1.5 l. of boiling alcohol. The mixture was refluxed for 1 hour afterwhich time it was refrigerated for 12 hours. The green solid whichseparated was collected and recrystallized three times from acetone,yielding 71 g. of product, M.P. 188- 190 C.

1-phenyl-3-methyl-4-keto-5-pyrazolone To a mixture of 145 g. of1-phenyl-3-methyl-4-(4- dimethylaminophenylimino)-5-pyrazolone in 2 l.of ethyl ether was added a solution of ml. of concentrated sulfuric acidin 1 liter of water. This mixture was stirred at room temperature for 1hour and filtered. The ether layer was separated, washed with water anddried over anhydrous magnesium sulfate. It was then concentrated invacuo and the residue was recrystallized from a 50:50 mixture of benzeneand ligroin, yielding 55 g. of product, M.P. 12l C.

1-phenyl-3-methyl-4-hydrazono-S-pyrazolone (Intermediate A) To asolution of 2 g. of l-phenyl-3-methyl-4-keto-5- pyrazolone in 20 ml. ofglacial acetic acid, which had been preheated on steam, was added asolution of 2 ml. of hydrazine hydrate in 5 ml. of glacial acetic acid.The resulting clear reaction mixture was heated on steam for 15 minutesafter which time it was poured into m1. of ice water whereupon a yellowsolid separated. The solid was collected and recrystallized fromligroin, yielding .5 g. of product, M.P. 103105 C.

1-phenyl-3-methyl-4-diazonium-S-pyrazolone (Intermediate B) To a mixtureof 5 g. of Intermediate A above, 11 g. of yellow mercuric oxide and 5 g.of anhydrous sodium sulfide in 200 ml. of ethyl ether was added 1.5 ml.of a saturated alcoholic potassium hydroxide solution. This mixture wasagitated at room temperature for 1 hour, filtered, and the filtrate wasconcentrated to dryness. The solid residue was recrystallized fromligroin, yielding 2 g. of product, M.P. 9799 C.

1-phenyl-3-methyl-4-acetoxy-S-pyrazolone A solution of 5 g. ofIntermediate B above and 2 ml. of fluoroboric acid (HBF in 25 ml. ofglacial acetic acid was heated on steam for 16 hours. This mixture wasthen poured into 100 ml. of ice water whereupon a solid separated, wascollected, and dried. This solid was recrystallized from aqueousacetonitrile, yielding 1.5 g. of product, M.P. -191 C.

Similarly any of the other couplers of Formula I are prepared as coupler1 starting in each instance with the appropriate four-equivalent parent5-pyrazolone coupler having the formula:

IV N=() R4 where R and R are as defined previously, then proceding withthe synthesis to form the corresponding 4- diazonium-S-pyrazolone andreacting it with the appropriate organic acid and acylating agent.

Coupler 2, for example, is prepared like coupler l by using 1 (2,4,6trichlorophenyl)-3-(4-nitroanilino)-5-pyrazolone as the parent couplerand reacting the corresponding 4-diazonium-S-pyrazolone with stearicacid.

Coupler 3 is prepared like coupler 1 by using the parent coupler l(2,4,6trichlorophenyl)-3-{3-[a-(2,4-di-tertamylphenoxy)acetamido]benzamido}S-pyrazolone and the acylating agent glacial acetic acid.

The preparation of my cyan-forming couplers of Formulas II and III isillustrated by the following preparation of coupler 7:

Intermediate A.-acetamido-4-benzyloxy-3-chloro- Z-methylphenol In 200volumes of dry acetone containing 6.5 g. of potassium carbonate wasplaced g. of 5-acetamido-3- chloro-2-methylhydroquinone and 8 g. ofu-bromotoluene. The mixture was refluxed for 1 /2 hours, cooled, pouredinto 500 volumes of an equivolume mixture of ether and 3% aqueous sodiumbicarbonate. The ether layer was withdrawn, dried, and then removedunder reduced pressure. The resulting solid was recrystallized fromacetonitrile, yielding 4.2 g. of product.

IntermediateB.2-benzyloXy-3-chloro-5-[a-(2,4-di-tertamylphenoxy)acetoxy]-4-methylacetanilideA solution of 3 g. of Intermediate A above and 7 g. ofu-(2,4-di-tert-amylphenoxy)acetic anhydride in 100 ml. of pyridine washeld at room temperature for 72 hours, after which time it was heated onsteam for /2 hour. The resultant solution was diluted with an equalvolume of ether, which Was then washed twice with dilute sodiumcarbonate solution. The ether layer was separated, dried, andconcentrated in vacuo. The residual oil was slurried in 150 ml. of waterand the solid which formed was filtered and air dried, yielding theproduct, M.P. 123- 126 C.

Coupler 7 A solution of 2 g. of Intermediate B above in 100 ml. of ethylacetate containing .1 g. of palladium on charcoal was reduced at 40 lb.p.s.i. hydrogen pressure, at room temperature. The solution wasfiltered, washed twice with dilute sodium carbonate solution, dried,concentrated in vacuo, yielding the product.

Coupler 9 is prepared by the method used for coupler 6 by starting withthe compound l,4-dihydroXy-N-[6-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide and then acylating it withacetic anhydride.

Couplers 4 (M.P. 162164 C.), 5 (M.P. 6263 C.) and 6 (M.P. 194 C.) wereprepared by the synthesis described by Wilt and Johnson Ber. 26, 1910;Olcott, J.A.C.S. 59, 392 (1937), and Desai and Sethna J. Ind. Chem. Soc.28, No. 4, 213-217 (1951), respectively.

Coupler 8 is prepared like coupler 6 by using stearoyl chloride in placeof acetic anhydride as the acylating agent.

Coupler 10 is prepared by reacting phenyl 1,4-di-hydroxy-2-naphthoate(formed by reacting 1,4-di-hydroxy- Z-naphthoic acid with phenol) withN-(3,5-di-carbomethoxyphenyl)-N-stearylamine to form 1,4-di-hydroxy- Noctadecyl-3,5-dicarbomethoXy-2-naphthanilide which is hydrolyzed, thenacetylated with acetic anhydride to produce 1 hydroxy4-acetoxy-N-octadecyl-3',5'-di-carbOXy-Z-naphthanilide.

The two-equivalent image-forming couplers of my invention aredistinguished from other two-equivalent couplers by having an acyloxygroup substituted on the coupling position of the coupler molecule. Mynondiffusing couplers are dispersed readily in emulsion layers as acoupler solvent solution having a wide range of coupler to solventratios.

My couplers are not only valuable for the reasons cited but becausephotographic emulsion layers color developed with them require only /2the amount of silver halide required by four-equivalent couplers. Ofparticular value are certain of my non-diffusing couplers which havehigh coupling reactivity when dispersed in photographic emulsion layerswithout any high-boiling solvent. These couplers are coated toadvantages in particularly thin layers that produce very sharp images.

The invention has been described in detail with particular reference topreferred embodiments thereof but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention as described hereinabove and as defined in the appendedclaims.

I claim:

1. An uncolored magenta-forming two-equivalent coupler selected fromthose having the formula:

wherein R represents unsubstituted alkyl having from 1 to 22 carbonatoms; R represents a group selected from the class consisting ofphenyl, 4-methylphenyl, 2,4,6-trichlorophenyl, 3,5-dibromophenyl andtrifiuoromethylphenyl; and R represents a group selected from the classconsisting of alkyl having from 1 to 22 carbon atoms, alkylamino inwhich the alkyl moiety has from 1 to 22 carbon atoms, phenylamino,tolylamino, 4-(3-sulfobenzamido)-phenylamino,trifiuoromethylphenylamino, 4-cyanophenylamino, 4-nitrophenylamino,phenylcarbonamido, 2,4,6-trichlorophenylcarbonamido,4-methylphenylcarbonamido, 2-ethoxyphenylcarbonamide, and3-[a-(2,4-di-tert-amylphenoXy)acetamid0]benzarnido.

2. An uncolored magneta-forming two-equivalent coupler selected fromthose having the formula:

wherein R represents unsubstituted alkyl having from 1 to 22 carbonatoms; R represents a group selected from the class consisting ofphenyl, 4-methylphenyl, 2,4,6-trichlorophenyl, 3,5-dibromophenyl andtrifluoromethylphenyl; and R represents a group selected from the classconsisting of methyl, 4-nitroanilino, and3-[u-(2,4-di-tertamylphenoxy)acetamido1benzarnido.

3. A two-equivalent magenta-forming coupler selected from the classconsisting of 1-phenyl-3-methyl-4-acetoxy- 5-pyrazolone,1-(2,4,6-trichlorophenyl)-3 (4 nitroanilino)-4-stearoyloxy-S-pyrazolone,and 1-(2,4,6-trichlorophenyl)-3-{3-[a-(2,4-di tertamylphenoxy)acetamido] benzamido}-4-acetoxy-5-pyrazolone.

4. The two-equivalent magenta-forming coupler 1-phenyl-3methyl-4-acetoxy-S-pyrazolone.

5. The two-equivalent magenta-forming coupler l-(2,4,6-trichlor0phenyl)-3-(4-nitroanilino)-4 stearoyloxy 5- pyrazolone.

'6. The two-equivalent magenta-forming coupler 1-(2,4,6-trichlorophenyl)-3-{3-[a-(2,4-di tert amylphenoxy)acetamido]benzamido}-4-acetoxy-5-pyrazolone.

(References on following page) 1 3 l 4 References Cited HENRY R. JILES,Primary Examiner. UNITED STATES PATENTS NATALIE TROUSOF, AssistantExaminer. 2,369,489 2/1945 Porter et a1. 260-310 OTHER REFERENCES 5Cornforth et al.: Jour. Chem. Soc. (London), 1953, pp. 0; 260287, 295,302, 304, 305, 307, 309, 93-98. 309.2, 470, 471, 473, 476, 479, 481,482, 484, 488, 326.13,

KOnek et al.: Chem. Abst. v01. 40, column 60634 326.14, 346.2, 347.4,347.5, 404, 410.5, 465, 468, 469 (1946).

H050 UNITED STATES PATENT OFFICE 569 CERTIFICATE OF CORRECTION PatentNo. 3 ,432 52l Dated March ll 1969 Inv nt fl Anthonv Loria It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 12, line LO, delete the term "oxyphenylcarbonamide" andsubstitute in its place --oxyphenylcarbonamido---; and line #2, deletethe term "magneta" and substitute in its place ---magenta---.

SEALED (SEAL) Attest:

Fletche WILLIAM E. soau m, JR. A fi Offi Commissioner of Patents

